Journal of Industrial and Engineering Chemistry 25 (2015) 176–179

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Kinetic study on the dilute acid catalyzed hydrolysis of waste

mushroom medium
Byeong-Il Na, Jae-Won Lee *
Department of Forest Products and Technology, College of Agriculture & Life Sciences, Chonnam National University, Buk-gu, Gwang-ju 500-757, South Korea

A R T I C L E I N F O A B S T R A C T

Article history: In this study, kinetic modeling for the acid hydrolysis of waste mushroom medium was investigated.
Received 12 May 2014 Sulfuric and oxalic acid were used as catalyst, under 140–160 8C at 50 mM acid concentration for 80 min.
Received in revised form 6 October 2014 Glucose was the most abundant sugar in the hydrolysate for both acid catalysts. The production of glucose
Accepted 18 October 2014
and xylose increased in proportion to reaction time until 150 8C. However, the sugar concentration increased
Available online 29 October 2014
in the initial stages at 160 8C and it has not increased after 10 min of reaction time, due to the degradation of
sugars to furfural and 5-hydroxymethylfurfural (HMF) at high temperature and long reaction time. The
Keywords:
activation energies for the degradation of xylan and glucan to xylose and glucose on oxalic acid catalyst were
Kinetic model
Acid hydrolysis
59.1 and 38.7 kJ/mol, respectively, which were lower values than that of sulfuric acid. The degradation
Waste mushroom medium reactions of xylose (105.4 kJ/mol) and glucose (128.2 kJ/mol) to furfural and HMF have high activation
Glucose energies, compared to those of xylan (69.1 kJ/mol) and glucan (50.0 kJ/mol) degradation on sulfuric acid
Xylose catalyst.
ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction terms to monosaccharide conversion for bio-based chemical

Biomass conversion promises to be an efficient and environ-
mentally responsible process for producing renewable fuels and
chemicals alternatives to petroleum. In particular, lignocellulosic
biomass is an attractive biomass to produce fuels and chemicals,
due to its abundance, and low price [1]. Lignocellulosic biomass
consists of cellulose, hemicellulose and lignin, and their relative
abundances depend on the type of biomass. Among those, cellulose
and hemicelluloses can be converted to monosaccharide, such as
glucose, xylose, arabinose, galactose and mannose, by thermo-
chemical or enzymatic hydrolysis. These monosaccharides are
widely known as basic chemicals for high value added chemical
production [2].
The waste mushroom medium is a lignocellulosic byproduct of
the commercial mushroom industry, and the total production was
approximately 1670,000 t annually in Korea [3]. Most mushroom
is cultivated artificially, using plastic pots filled with medium
material, such as lignocellulosic biomass and some additives. After
mushroom harvest, most of the waste mushroom medium is
usually discarded, as solid waste. Therefore, it has advantageous
* Corresponding author. Tel.: +82 625302098.
E-mail address: ljw43376@chonnam.ac.kr (J.-W. Lee).
production, since the waste mushroom still contains most of the
carbohydrate, after mushroom harvest.
In this study, waste mushroom medium of cauliflower
(Sparassis crispa) was used as lignocellulosic biomass. Cauliflower
mushroom is well known as a brown-rot fungus, which selectively
degrades the heartwood of wood. The production of cauliflower
mushroom is increasing in Korea, because of its anticancer and
immune activity [4]. Many researchers have reported the
utilization of waste mushroom medium as lignocellulosic biomass,
for value added chemicals production by hydrothermal treatment
[5–7]. Generally, dilute acid pretreatment has been widely used
for the monosaccharide production from lignocellulosic biomass.
However, monosaccharide is easy to degrade during acid
pretreatment, to produce some undesirable byproducts, such as
furfural, 5-hydroxymethylfurfural, formic acid, and levulinic acid
[8]. Those are widely known as fermentation inhibitors. Therefore,
an appropriate pretreatment condition is required, to increase
monosaccharide production, with low concentration of fermenta-
tion inhibitors.
In this study, we studied properties of the glucan and xylan
hydrolysis of waste mushroom medium, with two acid catalysts,
at different temperature. Based on those data, the reaction kinetic
was investigated, to obtain the maximum yield of glucose and
xylose.

http://dx.doi.org/10.1016/j.jiec.2014.10.030
1226-086X/ß 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
 B.-I. Na, J.-W. Lee / Journal of Industrial and Engineering Chemistry 25 (2015) 176–179 177

Experimental Where, k1 is the rate constant of xylose and glucose formation

(min1), and k2 is the reaction rate constant of xylose and glucose
Biomass degradation to furfural and HMF (min1).
The reaction rate constants (k1, k2) in the kinetic model were
Waste medium after cauliflower (Sparassis crispa) cultivation assumed by Arrhenius equation:
was used as biomass in this study. The medium for the cultivation of
cauliflower mushroom consisted of douglas fir sawdust 80%, wheat  
E
powder 10%, corn powder 10% and oligosaccharide 16 Brix. The k ¼ A exp
RT
biomass was provided from Jeonnam Forest Resources Research
Institute (Naju, Jeonnam, South Korea). Prior to hydrolysis, the
where A is the pre-exponential factor for lignocellulosic biomass
biomass was milled to pass a 40 mesh, using a Wiley mill J-NCM
hydrolysis (min1), E is the activation energy (kJ/mol), T is the
(JISICO, Korea), and stored at 4 8C, with less than 10% moisture
reaction temperature (K), and R is the universal gas constant
content.
(8.314 kJ/mol/K).

Dilute acid hydrolysis of biomass

Results and discussion

The hydrolysis was performed in oil bath, with temperature and

Hydrolysis of biomass
time control system. Each biomass (0.4 g/dry weight basis) and
acid solutions (50 mM) was placed in the glass reactor tube with a
The hydrolysis was performed at a temperature range of 140–
screw cap then heated to the desired temperature. The biomass/
160 8C, to investigate the different catalytic behavior on lignocel-
acid solution ratio was 1:10 (w/w). The reaction temperature and
lulosic biomass degradation. The raw material contained 28.8%
time ranged from 140 to 160 8C, and 0 to 80 min, respectively
lignin, 51.3% glucan and 11.2% xylan [11].
[9,10]. Oxalic and sulfuric acid were used as the acid catalyst in
Glucose was the most abundant sugar in the hydrolysate
this study.
obtained, under all experimental conditions. However, the xylose
released from hemicelluloses was relatively low. The waste medium
Analysis of hydrolysate
after cauliflower mushroom cultivation contained mostly cellulose
and lignin, since S. crispa as brown rot fungi secreted various
The sugars, furfural, and 5-hydroxymethylfurfural (HMF)
hemicellulases during cultivation, unlike other waste mushroom
concentrations in the hydrolysate were determined, using HPLC
medium [5,6]. Also, waste mushroom medium contained rich
(Waters 2695 system; Alliance, MA, USA), outfitted with an
glucan, such as mycelium of S. crispa and oligosaccharide. Therefore,
Aminex HPX-87H column (300  7.8 mm, Bio-Rad, Hercules, CA,
high glucose concentration was detected in hydrolysate in this study.
USA), and a refractive index detector (Waters 2414 system;
Fig. 1 shows the effect of reaction time and temperature on the
Alliance, MA, USA). The analysis was performed with 5 mM H2SO4
glucose and xylose production. The total sugar concentration
as the mobile phase at an isocratic flow rate of 0.3 mL/min, for
depended on both the reaction temperature and time. At 140 8C,
55 min. All samples were properly diluted and filtered through a
the glucose concentration increased with reaction time, on both
0.45 mm spin-filter before analysis, to remove particles. All
acid catalysts. On the other hand, the glucose concentration did not
analyses were carried out in triplicate.
increase, after reaching a maximum value at 160 8C. This was due
to the degradation of glucose to HMF at high temperature. The
Waste mushroom medium hydrolysis kinetic model
highest glucose concentration was 17.9 g/l, which was achieved
after 80 min of hydrolysis, at 150 8C with 50 mM sulfuric acid. The
The kinetic study of lignocellulosic biomass hydrolysis on acid
behavior of glucan hydrolysis slightly differed, depending on the
catalysts is difficult because the xylose, arabinose, glucose, furfural,
acid catalyst.
HMF, acetic acid, etc is produced by hydrolysis reaction. For this
The xylose concentration gradually increased, during hydro-
reason, pseudo homogeneous kinetic models are used to overcome
lysis at 140 8C and 150 8C with sulfuric acid. However, the trend of
the problem of the heterogeneity of the hydrolysate [9,10]. Lignocel-
xylose production was similar to that of glucose, when the
lulosic biomass hydrolysis by acid catalysts was on the hypothesis of
reaction temperature was 160 8C. The reason was that the high
pseudo homogeneous irreversible first-order reactions. In this study,
reaction temperature easily induced the degradation of xylose to
xylose and glucose oligomers were negligible during xylose and
furfural [2].
glucose formation. The model can be generalized as follows:
Fig. 2 shows the effect of reaction time and temperature on
furfural and HMF production, during dilute acid hydrolysis.
k1 k2
Xylan; Glucan !Xylose; Glucose!Degradation products Furfural and HMF, which are generated from hemicelluloses,
Oligomers were detected over all pretreatment conditions, in parallel to the

Fig. 1. Effect of temperature and reaction time on xylose and glucose production at different acid catalyst (OA: oxalic acid, SA: sulfuric acid, X: xylose, G: glucose).
178 B.-I. Na, J.-W. Lee / Journal of Industrial and Engineering Chemistry 25 (2015) 176–179

Fig. 2. Effect of temperature and reaction time on furfural and HMF production at different acid catalyst (OA: oxalic acid, SA: sulfuric acid, F: furfural, H: HMF).

formation of sugars. The furfural and HMF concentration increased
with the reaction time and temperature. However, the high
reaction temperature (160 8C) led to faster decomposition of
xylose and glucose. The HMF concentration generated from
glucose was relatively low, considering glucose production. The
reason is the different degradation rate between glucose to HMF,
and xylose to furfural. Xylose more easily degraded to furfural,
than glucose degraded to HMF, during acid hydrolysis [12]. This
result was similar to that of a previous study [13,14].
Kinetic study on biomass hydrolysis
The kinetic parameters for waste mushroom medium hydroly-
sis are presented in Tables 1 and 2. The estimated k1 values
increased with reaction temperature, which is related to the
degradation xylan to xylose and glucan to glucose. The highest
value of k1 was 0.72 min1 for the hydrolysis of glucan to glucose,
with sulfuric acid. The values of k1 for glucose formation differed,
depending on the acid catalysts, while the values of k1 for xylose
formation were similar, regardless of the acid catalysts.
The values of k1 were higher than the values of k2, over all
reaction temperature. It is implied that waste mushroom medium
hydrolysis to sugar is faster than sugar degradation. Some
researchers observed similar results for the acid hydrolysis of
hemicelluloses [15,16]. Comparing the values of k2 on acid
catalysts, sulfuric acid induced higher values of k2, than those of
oxalic acid. This implied that sulfuric acid catalyst more easily
produced sugar degradation products, than did oxalic acid catalyst.
This supports the suggestion made in an earlier study, that
dicarboxylic acid such as oxalic acid does not easily catalyze sugar
degradation [17,18]. On the whole, k2 values were lower than k1
Table 1
Value of k1 for waste mushroom medium hydrolysis at different acid catalyst and
temperature (unit: min1).
Temperature (8C) Xylan to xylose (k1) Glucan to glucose (k1)
Sulfuric acid Oxalic acid Sulfuric acid
140 0.015 0.017 0.031
150 0.030 0.032 0.051
160 0.048 0.046 0.072
values, regardless of acid catalyst. The rate constant for the k1 and
k2 depended on the reaction temperature.
The selective factor (k1/k2, the ratio of glucan and xylan
hydrolysis rate to glucose and xylose degradation rate) was used
to evaluate the hydrolysis efficiency [16,19]. Among the xylan
hydrolysis reaction, oxalic acid catalyst at 150 8C condition
resulted in the highest selectivity factor, at 3.56. For the glucan
hydrolysis reaction, the highest selectivity factor (k1/k2 = 6.25)
obtained when oxalic acid was used as catalyst at 140 8C. On the
other hand, the selectivity factors on sulfuric acid hydrolysis were
relatively low, compared to those of oxalic acid, which implied
that oxalic acid hydrolysis favored xylan and glucan hydrolysis
over xylose and glucose degradation, compared to those of
sulfuric acid.
The ln(k) versus 1/T curves were plotted, to calculate the kinetic
parameters (Fig. 3). The apparent activation energies were
calculated using Arrhenius plots, for sulfuric and oxalic acid
between 140 and 160 8C. The correlated activation energy and pre-
exponential constant are shown in Table 3. The R2 value was high,
at more than 0.94 on the hydrolysis and degradation process. This
indicated that a fine fit was achieved between the experimental
data and the kinetic model.
In this study, most of the activation energies for xylan and glucan
hydrolysis were similar to other reported data for lignocellulosic
biomass (44–180 kJ/mol). They were lower than those for most
other lignocellulosic biomass reported in the literature [2,10,20].
The lower activation energy suggested that waste mushroom
medium could easily produce fermentable sugars.
The activation energies for xylan and glucan degradation on
oxalic acid catalyst were 59.1 and 38.7 kJ/mol, respectively, which
were lower values than those of sulfuric acid. This implied that the
reaction rate of xylan and glucan conversion to xylose and glucose
on oxalic acid was slightly faster than those of sulfuric acid. The
reaction rates of the xylose and glucose degradation to furfural and
HMF on sulfuric acid were low, compared to those of oxalic acid.
The degradation reaction of xylose and glucose to furfural and HMF
has high activation energies, compared to those of xylan and
Oxalic acid glucan degradation, which implied that acid hydrolysis more easily
0.025 induced the production of fermentable sugars, than degradation
0.045 products.
0.048

Conclusions

Table 2
Oxalic acid presented high hydrolysis efficiency for the
Value of k2 for waste mushroom medium hydrolysis at different acid catalyst and production of glucose and xylose. The activation energies for
temperature (unit: min1). xylan and glucan degradation on oxalic acid catalyst had lower
Temperature (8C) Xylose to furfural (k2) Glucose to HMF (k2)
values, than those of sulfuric acid. This implied that oxalic acid
hydrolysis favored the degradation of xylan and glucan to xylose
Sulfuric acid Oxalic acid Sulfuric acid Oxalic acid
and glucose, compared to those of sulfuric acid. Oxalic acid could
140 0.008 0.006 0.006 0.004 induce a high concentration of fermentable sugar, and minimize
150 0.014 0.009 0.014 0.009
sugar degradation products during hydrolysis (140 8C), compared
160 0.047 0.016 0.053 0.023
to those in sulfuric acid hydrolysis. The results can be used as a
 B.-I. Na, J.-W. Lee / Journal of Industrial and Engineering Chemistry 25 (2015) 176–179 179

Fig. 3. Arrhenius plot of xylan, glucan hydrolysis and xylose, glucose degradation for 50 mM sulfuric and oxalic acid ((A) xylan to xylose, (B) glucan to glucose, (C) xylose to
furfural, (D) glucose to HMF).

National Research Foundation of Korea (NRF) funded by the

Table 3 Ministry of Education, Science and Technology (2010-0020141).
Kinetic parameters for waste mushroom medium hydrolysis.

Hydrolysis or Acid catalysts Pre-exponential Activation R2 References

degradation factor (min1) energy
(kJ/mol) [1] P. Ghosh, A. Singh, Adv. Appl. Microbiol. 39 (1993) 295.
[2] X. Liu, M. Lu, N. Ai, F. Yu, J. Ji, Ind. Crop Prod. 38 (2012) 81.
7
Xylan to xylose Sulfuric acid 2.30  10 69.1 0.99 [3] Statistical Yearbook of Forestry, Statistical Yearbook of Forestry, Korea Forest
Oxalic acid 1.16  1011 59.1 0.98 Service, 2005.
Glucan to glucose Sulfuric acid 2.74  105 50.0 0.94 [4] H. Kim, J. Kim, H. Ryu, H. Park, Y. Kim, J. Kang, H. Kim, J. Hong, Y. Kim, S. Han, Int.
Oxalic acid 3.95  106 38.7 0.96 Immunopharmacol. 10 (2010) 1284.
Xylose to furfural Sulfuric acid 2.58  1012 105.1 0.97 [5] N. Sato, K. Shinji, M. Mizuno, K. Nozaki, M. Suzuki, S. Makishima, M. Shiroishi, T.
Oxalic acid 6.73  105 58.2 0.99 Onoda, F. Takahashi, T. Kanda, Bioresour. Technol. 101 (2010) 6006.
Glucose to HMF Sulfuric acid 3.13  1015 128.2 0.98 [6] C. Asada, A. Asakawa, C. Sasaki, Y. Nakamura, Bioresour. Technol. 102 (2011)
Oxalic acid 9.31  1011 103.9 0.99 10052.
[7] N. Kapu, M. Manning, T. Hurley, J. Voigt, D. Cosgrove, C. Romanine, Bioresour.
Technol. 114 (2012) 399.
[8] L. Jonsson, B. Alriksson, N. Nilvebrant, Biotechnol. Biofuels 6 (2013) 1.
[9] J. Seaman, Ind. Eng. Chem. 37 (1945) 43.
guide for optimization the reaction conditions to obtain high [10] S. Yat, A. Berger, D. Shonnard, Bioresour. Technol. 99 (2008) 3855.
yields of fermentable sugars. [11] Y. Seo, D. Oh, J. Lee, J. Ind. Eng. Chem. 19 (2013) 1535.
[12] E. Sjöstrom, Wood Chemistry: Fundamentals and Application, Academic press,
New York, NY, 1981.
Acknowledgements [13] B. Girisuta, K. Dussan, D. Haverty, J. Leahy, M. Hayes, Chem. Eng. J. 217 (2013) 61.
[14] H. Lee, W. Lim, J. Lee, J. Ind. Eng. Chem. 19 (2013) 2010.
[15] Y. Arslan, S. Takac, N. Eken-Saracoglu, Chem. Eng. J. 185 (2012) 23.
This research was supported by Basic Science Research Program [16] Q. Jin, H. Zhang, L. Yan, L. Qu, H. Huang, Biomass Bioenergy 35 (2011) 4158.
through the National Research Foundation of Korea (NRF) funded [17] A. Kootstra, H. Beeftink, E. Scott, J. Sanders, Biochem. Eng. J. 46 (2009) 126.
by the Ministry of Education, Science and Technology (2011- [18] W. Lim, J. Lee, Bioresour. Technol. 140 (2013) 206.
[19] Y. Lu, N. Mosier, Biotechnol. Bioeng. 101 (2008) 1170.
0021971) and by Priority Research Centers Program through the [20] A. Yeşim, T. Serpil, E. Nurdan, Chem. Eng. J. 185 (2011) 23.